WO2014126061A1 - Procédés respectivement pour la production de composé de type sel de type carbonate et de matière active d'électrode positive - Google Patents

Procédés respectivement pour la production de composé de type sel de type carbonate et de matière active d'électrode positive Download PDF

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WO2014126061A1
WO2014126061A1 PCT/JP2014/053085 JP2014053085W WO2014126061A1 WO 2014126061 A1 WO2014126061 A1 WO 2014126061A1 JP 2014053085 W JP2014053085 W JP 2014053085W WO 2014126061 A1 WO2014126061 A1 WO 2014126061A1
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carbonate
sulfate
positive electrode
ratio
mol
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PCT/JP2014/053085
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Japanese (ja)
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酒井　智弘
翼 高杉
拓也 寺谷
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旭硝子株式会社
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Priority to JP2015500233A priority Critical patent/JP6328096B2/ja
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Priority to US14/798,565 priority patent/US9643859B2/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a carbonate compound, a method for producing a positive electrode active material, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
  • Lithium ion secondary batteries are widely used in portable electronic devices such as mobile phones and notebook computers.
  • a positive electrode active material of a lithium ion secondary battery a positive electrode active material (LiCoO 2 , LiNiO 2 , LiNi 0.8 Co 0.2 O 2 , LiMn 2 O 4, etc.) made of a composite oxide containing Li and a transition metal element .)It has been known.
  • Non-Patent Document 1 a transition metal element sulfate such as Mn sulfate and a carbonate such as sodium carbonate were mixed in an aqueous solution to obtain a carbonate compound containing a transition metal element. Thereafter, a method is known in which the carbonate compound and lithium carbonate are mixed and baked (Non-Patent Document 1).
  • Non-Patent Document 1 In the production of the positive electrode active material using the method as described in Non-Patent Document 1, particularly when the Mn ratio is lowered to increase the discharge capacity, the particle diameter and particle shape of the positive electrode active material are likely to be non-uniform, Moreover, a hollow part is easy to be formed in a positive electrode active material.
  • the positive electrode active material is rapidly deteriorated, and it is possible to obtain a lithium ion secondary battery having excellent characteristics (hereinafter, also referred to as “cycle characteristics”) that are difficult to decrease the discharge capacity and the average discharge voltage after repeated charge / discharge cycles. Have difficulty.
  • the present invention provides a method for producing a carbonate compound and a positive electrode active material that can provide excellent cycle characteristics. Moreover, this invention provides the positive electrode for lithium ion secondary batteries and lithium ion secondary battery using the positive electrode active material obtained by the said manufacturing method.
  • the gist of the present invention is as follows. (1) The following sulfate (A) and the following carbonate (B) are mixed in the state of an aqueous solution, and the Mn ratio with respect to the total of Ni, Co and Mn contained in the sulfate (A) at the start of the mixing is 65 mol. Carbon dioxide having a Mn ratio of 33.3 to 65 mol%, a Ni ratio of 17.5 to 50 mol%, and a Co ratio of 0 to 33.3 mol% with respect to the total of Ni, Co and Mn in the overall average composition. The manufacturing method of the carbonate compound which deposits a salt compound.
  • Sulfate (A) Sulfate composed of Mn sulfate and Ni sulfate, or sulfate composed of Mn sulfate, Ni sulfate and Co sulfate.
  • Carbonate (B) At least one carbonate selected from the group consisting of sodium carbonate and potassium carbonate.
  • the Mn ratio of the sulfate (A) is more than 65 mol% and 100 mol% or less, the Ni ratio is 0 to 35 mol%, and the Co ratio is 0 to 33.3 mol%.
  • a method for producing a carbonate compound is more than 65 mol% and 100 mol% or less, the Ni ratio is 0 to 35 mol%, and the Co ratio is 0 to 33.3 mol%.
  • the positive electrode for lithium ion secondary batteries containing the positive electrode active material obtained by the manufacturing method of description, a electrically conductive material, and a binder.
  • a lithium ion secondary battery comprising the lithium ion secondary battery positive electrode according to (10), a negative electrode, and a nonaqueous electrolyte.
  • the method for producing a carbonate compound of the present invention it is possible to produce a carbonate compound that provides a positive electrode active material capable of obtaining excellent cycle characteristics. According to the method for producing a positive electrode active material of the present invention, a positive electrode active material capable of obtaining excellent cycle characteristics can be produced. If the positive electrode for lithium ion secondary batteries of this invention is used, the lithium ion secondary battery excellent in cycling characteristics will be obtained. The lithium ion secondary battery of the present invention is excellent in cycle characteristics.
  • the method for producing a carbonate compound of the present invention has a Mn ratio of 33.3 to 65 mol%, a Ni ratio of 17.5 to 50 mol%, and a Co ratio of 0 to 33 with respect to the total of Ni, Co and Mn in the overall average composition.
  • This is a method for producing a carbonate compound of 3 mol%.
  • Mn, Ni and Co may be collectively referred to as transition metal element (X).
  • the sulfate (A) is a sulfate comprising Mn sulfate and Ni sulfate, or a sulfate comprising Mn sulfate, Ni sulfate and Co sulfate.
  • Mn include manganese sulfate (II) pentahydrate, manganese sulfate (II) ammonium hexahydrate, and the like.
  • Examples of Ni sulfate include nickel sulfate (II) hexahydrate, nickel sulfate (II) heptahydrate, nickel sulfate (II) ammonium hexahydrate, and the like.
  • Examples of the sulfate of Co include cobalt (II) sulfate heptahydrate and cobalt (II) ammonium sulfate hexahydrate.
  • a sulfate of another metal element (M ′) other than Ni, Co and Mn may be used.
  • the other metal element (M ′) sulfate is preferably at least one selected from the group consisting of Mg sulfate, Ca sulfate, Sr sulfate, Ba sulfate, and Al sulfate.
  • the aqueous solution of sulfate (A) may be two or more kinds of aqueous solutions separately containing each of the two or more kinds of sulfates (A). It is good also as 1 type of aqueous solution containing the above sulfate (A). Moreover, you may use together the aqueous solution containing 1 type of sulfates (A), and the aqueous solution containing 2 or more types of sulfates (A). The same applies when two types of carbonate (B) are used.
  • the method for producing a carbonate compound of the present invention is characterized in that the Mn ratio relative to the total of Ni, Co and Mn contained in the sulfate (A) at the start of mixing is more than 65 mol%. That is, in the method for producing a carbonate compound of the present invention, sulfate (A) and carbonate (B) are prepared using sulfate (A) having a Mn ratio of more than 65 mol% with respect to the total of Ni, Co and Mn. Are mixed in an aqueous solution state to start precipitation of a carbonate compound (hereinafter referred to as “pre-precipitation step”).
  • the sulfate (A) needs to have a Mn ratio of at least 65 mol% with respect to the total of Ni, Co, and Mn.
  • the ratio of Mn to the sum of Ni, Co and Mn of sulfate (A) in the post-precipitation step may be constant, or may be decreased continuously or intermittently.
  • the Mn ratio may be higher than the Mn ratio at the start of mixing.
  • the Mn ratio in the sulfate (A) is preferably constant at less than 65 mol%. Furthermore, in the production method of the present invention, the pre-precipitation step and the post-precipitation step may decrease the Mn ratio continuously or intermittently.
  • a precipitation reaction in which the Mn ratio of the sulfate (A) is further fixed to the target ratio is performed, and the carbonate compound is grown until a desired particle size is obtained. It is preferable.
  • the particle diameter of the carbonate compound after controlling the Mn ratio it becomes easier to control the particle diameter of the carbonate compound as compared with the case of simultaneously controlling the Mn ratio and the particle diameter.
  • the concentration of carbonate (B) in the aqueous solution of carbonate (B) is preferably from 0.1 to 2 mol / kg, more preferably from 0.5 to 2 mol / kg. If the concentration of the carbonate (B) is within the above range, the carbonate compound is likely to precipitate. When using 2 or more types of aqueous solution containing a sulfate (B), it is preferable to make the density
  • the solvent used in the aqueous solution of sulfate (A) and carbonate (B) may be water alone as long as sulfate (A) and carbonate (B) are dissolved.
  • an aqueous medium containing components other than water examples include methanol, ethanol, 1-propanol, 2-propanol, polyol and the like.
  • the polyol examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, butanediol, glycerin and the like.
  • the temperature of the mixed solution when mixing the sulfate (A) and the carbonate (B) is preferably 20 to 80 ° C., more preferably 25 to 60 ° C., because the carbonate compound is likely to precipitate. Further, when the sulfate (A) and the carbonate (B) are mixed, it is preferable to perform the mixing under a nitrogen atmosphere or an argon atmosphere from the viewpoint of suppressing the oxidation of the precipitated carbonate compound. From the viewpoint, it is particularly preferable to perform the mixing in a nitrogen atmosphere.
  • the specific surface area of the carbonate compound is preferably 50 ⁇ 300m 2 / g, particularly preferably 100 ⁇ 250m 2 / g.
  • the specific surface area of the positive electrode active material can be easily controlled within a preferable range described later, and a positive electrode active material exhibiting a high discharge capacity can be easily obtained.
  • the specific surface area of the carbonate compound is measured by the method described in the examples.
  • the particle size and particle shape of the obtained carbonate compound are likely to be non-uniform, and a carbonate compound having a hollow portion is likely to be formed by collecting particles with irregular shapes formed by aggregation at the initial stage of the reaction. Conceivable.
  • the agglomeration of the transition metal element carbonate at the initial stage of the reaction is suppressed by keeping the Mn ratio in the sulfate (A) as high as more than 65 mol% in the initial stage of the precipitation reaction. Is done.
  • a carbonate compound obtained by the above production method and lithium carbonate are mixed and fired at 500 to 1000 ° C. to obtain a positive electrode active material.
  • Examples of the method of mixing the carbonate compound and lithium carbonate include a method using a rocking mixer, a nauta mixer, a spiral mixer, a cutter mill, a V mixer, and the like.
  • An electric furnace, a continuous firing furnace, a rotary kiln or the like can be used for the firing apparatus. Since the carbonate compound is oxidized during firing, the firing is preferably performed in the air, and particularly preferably performed while supplying air.
  • the air supply rate is preferably 10 to 200 mL / min, more preferably 40 to 150 mL / min per liter of the furnace internal volume.
  • the firing may be one-stage firing at 500 to 1000 ° C., or two-stage firing in which main firing is performed at 700 to 1000 ° C. after preliminary firing at 400 to 700 ° C.
  • two-stage firing is preferable because Li easily diffuses uniformly into the positive electrode active material.
  • the temperature for temporary firing is preferably 400 to 700 ° C, more preferably 500 to 650 ° C.
  • the temperature of the main firing in the case of two-stage firing is preferably 700 to 1000 ° C., and more preferably 800 to 950 ° C.
  • the Mn ratio may be constant, or the Mn ratio may decrease continuously or intermittently toward the outside. Further, in the high concentration region (H), there may be a portion where the Mn ratio increases continuously or intermittently toward the outside. Especially, it is preferable that Mn ratio of a high concentration area
  • the Ni ratio, the Co ratio, and the Mn ratio in the transition metal element in the low concentration region (L) are the ranges described above for the total ratio of Ni, Co, and Mn, the Ni ratio, and the Co ratio in the average composition of the positive electrode active material. Adjust to be inside.
  • the Mn ratio may be constant, or the Mn ratio may decrease continuously or intermittently toward the outside.
  • the low concentration region (L) there may be a portion where the Mn ratio increases continuously or intermittently toward the outside.
  • the positive electrode active material is preferably a compound (1) represented by the following formula (1).
  • M ' is at least 1 sort (s) chosen from the group which consists of Mg, Ca, Sr, Ba, and Al.
  • a to e are 0.1 ⁇ a ⁇ 0.4, 0.175 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.333, 0.333 ⁇ d ⁇ 0.65, and 0 ⁇ e ⁇ 0.05, respectively.
  • f is a numerical value determined by the valences of Li, Ni, Co, Mn, and M ′.
  • a of the compound (1) is a positive electrode active material having a high initial discharge capacity and initial discharge voltage, 0.1 ⁇ a ⁇ 0.25 is more preferable.
  • b is preferably 0.277 ⁇ b ⁇ 0.5, particularly preferably 0.337 ⁇ b ⁇ 0.5, for the same reason as a.
  • c of the compound (1) is more preferably 0 ⁇ c ⁇ 0.2, and particularly preferably 0 ⁇ c ⁇ 0.133.
  • d is more preferably 0.4 ⁇ d ⁇ 0.65 and particularly preferably 0.433 ⁇ d ⁇ 0.6 for the same reason as a.
  • e is more preferably 0.001 ⁇ e ⁇ 0.05, particularly preferably 0.001 ⁇ e ⁇ 0.02, from the viewpoint of excellent initial discharge capacity and cycle characteristics.
  • the positive electrode for a lithium ion secondary battery of the present invention has a positive electrode current collector and a positive electrode active material layer provided on the positive electrode current collector.
  • a known embodiment can be adopted except that the positive electrode active material obtained by the production method of the present invention is used.
  • binder examples include fluorine-based resins (polyvinylidene fluoride, polytetrafluoroethylene, etc.), polyolefins (polyethylene, polypropylene, etc.), polymers having unsaturated bonds, and copolymers (styrene-butadiene rubber, isoprene rubber). , Butadiene rubber, etc.), acrylic acid polymers and copolymers (acrylic acid copolymers, methacrylic acid copolymers, etc.).
  • the binder may be one type or two or more types.
  • the positive electrode active material may be one type or two or more types.
  • thickener examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and polyvinylpyrrolidone.
  • One thickener may be used, or two or more thickeners may be used.
  • the manufacturing method of the positive electrode for lithium ion secondary batteries can employ
  • the following method is mentioned as a manufacturing method of the positive electrode for lithium ion secondary batteries.
  • a positive electrode active material, a conductive material and a binder are dissolved or dispersed in a medium to obtain a slurry, or a positive electrode active material, a conductive material and a binder are kneaded with a medium to obtain a kneaded product.
  • the positive electrode active material layer is formed by coating the obtained slurry or kneaded material on the positive electrode current collector.
  • the negative electrode is formed by forming a negative electrode active material layer containing a negative electrode active material on a negative electrode current collector.
  • the negative electrode current collector include metal foils such as nickel foil and copper foil.
  • the negative electrode active material may be any material that can occlude and release lithium ions at a relatively low potential.
  • an oxide mainly composed of lithium metal, lithium alloy, carbon material, periodic table 14 or group 15 metal. Silicon carbide compounds, silicon oxide compounds, titanium sulfide, boron carbide compounds and the like.
  • iron oxide, ruthenium oxide, molybdenum oxide, tungsten oxide, titanium oxide, tin oxide, and other oxides and other nitrides may be used as the negative electrode active material.
  • Examples of the carbon material for the negative electrode active material include non-graphitizable carbon, artificial graphite, natural graphite, pyrolytic carbons, cokes (pitch coke, needle coke, petroleum coke, etc.), graphites, and glassy carbons.
  • Organic polymer compound fired bodies obtained by firing and polymerizing organic polymer compounds (phenol resin, furan resin, etc.) at an appropriate temperature, carbon fibers, activated carbon, carbon blacks and the like.
  • Examples of the metal of Group 14 of the periodic table include Si and Sn. Among these, Si is preferable as the metal of Group 14 of the periodic table.
  • non-aqueous electrolyte examples include a non-aqueous electrolyte obtained by dissolving an electrolyte salt in an organic solvent, a solid electrolyte containing an electrolyte salt, a solid electrolyte obtained by mixing or dissolving an electrolyte salt in a polymer electrolyte, a polymer compound, and the like. Or a gel electrolyte etc. are mentioned.
  • any material having lithium ion conductivity may be used, and either an inorganic solid electrolyte or a polymer solid electrolyte may be used.
  • the inorganic solid electrolyte include lithium nitride and lithium iodide.
  • the polymer solid electrolyte include an electrolyte containing an electrolyte salt and a polymer compound that dissolves the electrolyte salt.
  • the polymer compound that dissolves the electrolyte salt include ether polymer compounds (poly (ethylene oxide), cross-linked poly (ethylene oxide), etc.), poly (methacrylate) ester polymer compounds, and acrylate polymer compounds. Etc.
  • Examples of the monomer copolymerized with polyethylene oxide include methyl methacrylate, butyl methacrylate, methyl acrylate, and butyl acrylate.
  • a fluorine-based polymer compound is particularly preferable among the polymer compounds from the viewpoint of stability against redox reaction.
  • the shape of the lithium ion secondary battery is not particularly limited, and shapes such as a coin shape, a sheet shape (film shape), a folded shape, a wound type bottomed cylindrical shape, a button shape, and the like can be appropriately selected depending on the application.
  • Example 1 (Production of carbonate compounds) Nickel sulfate (II) hexahydrate, cobalt sulfate (II) heptahydrate and manganese sulfate (II) pentahydrate have a molar ratio of Ni, Co and Mn as shown in Table 1.
  • aqueous sulfate solutions 1-1 and 1-2 were prepared by dissolving in distilled water so that the total amount of sulfate was 1.5 mol / kg. Further, 0.92 kg of sodium carbonate was dissolved in 4.88 kg of distilled water to prepare a 5.8 kg carbonate aqueous solution (pH adjusting solution).
  • distilled water is placed in a 2 L baffled glass mixing tank, heated to 50 ° C. with a mantle heater, and stirred with a paddle type stirring blade, and the aqueous sulfate solution 1-1 is added at a rate of 10.0 g / min. 3 hours, then sulfate aqueous solution 1-2 was added for 3 hours.
  • an aqueous carbonate solution pH adjusting solution
  • the ratio of Ni, Co, and Mn in the charged amount of the sulfate aqueous solution in the precipitation reaction was as shown in Table 3.
  • the liquid was continuously extracted using a filter cloth so that the amount of liquid in the mixing tank did not exceed 2 L.
  • pressure filtration and dispersion in distilled water were repeated to wash the carbonate compound. The washing was terminated when the electrical conductivity of the supernatant liquid reached 20 mS / m, and dried at 120 ° C. for 15 hours to obtain a carbonate compound.
  • Nickel sulfate (II) hexahydrate, cobalt sulfate (II) heptahydrate and manganese sulfate (II) pentahydrate have a molar ratio of Ni, Co and Mn as shown in Table 1.
  • 4 kg of aqueous sulfate solution 1-3 was prepared by dissolving in distilled water so that the total amount of sulfate was 1.5 mol / kg. Further, 0.92 kg of sodium carbonate was dissolved in 4.88 kg of distilled water to prepare a 5.8 kg carbonate aqueous solution (pH adjusting solution). Next, distilled water is put into a 2 L glass baffle with a baffle, heated to 30 ° C.
  • Nickel sulfate (II) hexahydrate, cobalt sulfate (II) heptahydrate and manganese sulfate (II) pentahydrate have a molar ratio of Ni, Co and Mn as shown in Table 2.
  • 2 kg, 4.5 kg, and 3 kg of aqueous sulfate solutions 2-1, 2-2, and 2-3 were prepared by dissolving in distilled water so that the total amount of sulfate was 1.5 mol / kg. did.
  • 1.9 kg of sodium carbonate was dissolved in 10.1 kg of distilled water to prepare 12 kg of an aqueous carbonate solution (pH adjusting solution).
  • Example 4 In the same manner as in Example 3, 4.5 kg of an aqueous sulfate solution 2-3 was prepared. In addition, 1.9 kg of sodium carbonate was dissolved in 10.1 kg of distilled water to prepare 12 kg of an aqueous carbonate solution (pH adjusting solution). Next, distilled water was put into a 2 L glass baffle with baffle, heated to 30 ° C. with a mantle heater, and stirred with a paddle type stirring blade, while only 5.0 g / A carbonate compound was prepared in the same manner as in Example 3 except that it was added at a rate of 14 minutes for 14 minutes. Moreover, the positive electrode active material was obtained like Example 3 using the said carbonate compound.
  • Example 5 A carbonate compound was produced in the same manner as in Example 4 except that the aqueous sulfate solution 2-3 was added at a rate of 2.5 g / min for 28 hours. Moreover, the positive electrode active material was obtained like Example 3 using the said carbonate compound.
  • Example 1 in which the Mn ratio in the sulfate aqueous solution in the initial stage of mixing was more than 65 mol%, compared with Example 2 in which the Mn ratio was 65 mol% or less, the carbonate compound and the positive electrode active material A carbonate compound and a positive electrode active material having a small D 90 / D 10 and a more uniform particle diameter were obtained. Moreover, in Example 1, the specific surface area of the carbonate compound and the positive electrode active material was smaller than that of Example 2, and a good carbonate compound and positive electrode active material having a nearly spherical particle shape were obtained.
  • Example 3 in which the Mn ratio in the sulfate aqueous solution at the initial stage of mixing was more than 65 mol%, carbonate having a uniform particle diameter and a good particle shape was compared with Example 4 in which the Mn ratio was 65 mol% or less. A compound and a positive electrode active material were obtained.
  • Example 5 in which the Mn ratio in the sulfate aqueous solution at the initial stage of mixing was 65 mol% or less and the addition time was made equal to Example 3, D 90 / D 10 was hardly improved.
  • the obtained positive electrode sheet was punched into a circular shape with a diameter of 18 mm as a positive electrode, and a stainless steel simple sealed cell type lithium ion secondary battery was assembled in a glove box under argon.
  • a stainless steel plate having a thickness of 1 mm was used as the negative electrode current collector, and a metal lithium foil having a thickness of 500 ⁇ m was formed on the negative electrode current collector to form a negative electrode.
  • porous polypropylene having a thickness of 25 ⁇ m was used as the separator.
  • the obtained lithium ion secondary battery was connected to a charge / discharge evaluation device (manufactured by Toyo System Co., Ltd., device name: TOSCAT-3000) and charged to 4.6 V at a load current of 20 mA per 1 g of the positive electrode active material.
  • An activation treatment was performed by discharging to 2.0 V at a load current of 20 mA per 1 g of the active material.
  • a charge / discharge cycle of charging to 4.5 V at a load current of 200 mA per 1 g of the positive electrode active material and discharging to 2.0 V at a load current of 200 mA per 1 g of the positive electrode active material was repeated 110 times.
  • the discharge capacity at the time of activation processing is “initial discharge capacity”
  • the discharge capacity at 110th cycle is “post-cycle discharge capacity”
  • the ratio of post-cycle discharge capacity to the third cycle discharge capacity is “discharge capacity maintenance ratio”. did.
  • Table 4 shows the measurement results of the initial discharge capacity and discharge capacity retention rate in each example.
  • Example 1 where the positive electrode active material was obtained by the production method of the present invention, a carbonate precipitation reaction was initiated using a sulfate having a Mn ratio of 65 mol% or less, and a positive electrode active material having an equivalent composition was obtained.
  • the cycle characteristics were excellent compared to Example 2 where the material was obtained.
  • Example 1 which obtained the positive electrode active material by the manufacturing method of this invention also started mixing using the sulfate whose Mn ratio is 65 mol% or less, and compared with Example 4 which obtained the positive electrode active material of the equivalent composition. The cycle characteristics were excellent. Also in Example 3, a sufficient initial discharge capacity was obtained.
  • Example 3 was excellent in cycle characteristics. As shown in FIGS. 1 and 2, the positive electrode active material of Example 5 was formed with a hollow portion, whereas the positive electrode active material of Example 3 was not formed with a hollow portion. As described above, according to the production method of the present invention, a positive electrode active material having a uniform particle size and a good particle shape, in which the formation of hollow portions is suppressed, and an excellent cycle can be obtained by using the positive electrode active material. A lithium ion secondary battery having characteristics was obtained.
  • the carbonate compound obtained by the production method of the present invention by using the carbonate compound obtained by the production method of the present invention, it is possible to obtain a positive electrode active material having a uniform particle diameter and good particle shape, and suppressing the formation of hollow portions. Therefore, a lithium ion secondary battery having a sufficient discharge capacity and excellent cycle characteristics can be obtained.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

L'invention porte sur un composé de type sel de type carbonate et sur une matière active d'électrode positive, qui permettent la production d'une batterie secondaire au lithium-ion ayant une excellente propriété de cycle. L'invention porte également sur un procédé pour la production d'un composé de type sel de type carbonate, qui comprend le mélange d'un sel de type sulfate (A) comprenant un sel de type sulfate de Mn et un sel de type sulfate de Ni ou comprenant un sel de type sulfate de Mn, un sel de type sulfate de Ni et un sel de type sulfate de Co, avec un sel de type carbonate (B) comprenant du carbonate de sodium et/ou du carbonate de potassium dans une solution aqueuse pour faire précipiter un composé de type sel de type carbonate ayant une teneur en Mn de 33,3 à 65 % en mole, une teneur en Ni de 17,5 à 50 % en mole et une teneur en Co de 0 à 33,3 % en mole, le tout par rapport à la quantité totale de Ni, Co et Mn dans la composition moyenne du corps entier du composé de type sel de type carbonate, le rapport de la quantité de Mn sur la quantité totale de Ni, Co et Mn dans le sel de type sulfate (A) au moment du début du mélange étant réglé à une valeur supérieure à 65 % en mole. L'invention porte également sur un procédé pour la production d'une matière active d'électrode positive, qui comprend le mélange d'un composé de type sel de type carbonate produit par le procédé susmentionné avec du carbonate de lithium et ensuite la combustion du mélange ainsi obtenu à une température de 500 à 1000°C.
PCT/JP2014/053085 2013-02-14 2014-02-10 Procédés respectivement pour la production de composé de type sel de type carbonate et de matière active d'électrode positive WO2014126061A1 (fr)

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US11952287B2 (en) 2016-07-20 2024-04-09 Haldor Topsøe A/S Method for the precipitation of particles of a metal carbonate material without use of a chelating agent
CN110492097B (zh) * 2019-08-30 2021-04-27 中南大学 一种ncm三元复合正极材料及其制备和应用

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